WO2017207555A1 - Preparation of mesoporous carbon with catalytically active metal oxide nanoparticles for the selective hydrogenation of alpha-beta-unsaturated aldehydes - Google Patents
Preparation of mesoporous carbon with catalytically active metal oxide nanoparticles for the selective hydrogenation of alpha-beta-unsaturated aldehydes Download PDFInfo
- Publication number
- WO2017207555A1 WO2017207555A1 PCT/EP2017/063012 EP2017063012W WO2017207555A1 WO 2017207555 A1 WO2017207555 A1 WO 2017207555A1 EP 2017063012 W EP2017063012 W EP 2017063012W WO 2017207555 A1 WO2017207555 A1 WO 2017207555A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- mesoporous carbon
- metal
- carbon structure
- nanoparticles
- loaded
- Prior art date
Links
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title claims abstract description 88
- 239000002105 nanoparticle Substances 0.000 title claims abstract description 39
- 229910044991 metal oxide Inorganic materials 0.000 title claims abstract description 35
- 150000004706 metal oxides Chemical class 0.000 title claims abstract description 35
- 150000001299 aldehydes Chemical class 0.000 title abstract description 16
- 238000005984 hydrogenation reaction Methods 0.000 title description 8
- 238000002360 preparation method Methods 0.000 title description 3
- 229910052751 metal Inorganic materials 0.000 claims abstract description 32
- 239000002184 metal Substances 0.000 claims abstract description 32
- 238000000034 method Methods 0.000 claims abstract description 31
- 239000003054 catalyst Substances 0.000 claims abstract description 17
- 150000001298 alcohols Chemical class 0.000 claims abstract description 11
- 238000004519 manufacturing process Methods 0.000 claims abstract description 10
- 238000009901 transfer hydrogenation reaction Methods 0.000 claims abstract description 9
- 229920000642 polymer Polymers 0.000 claims description 39
- -1 poly(ethylene oxide) Polymers 0.000 claims description 23
- 150000001491 aromatic compounds Chemical class 0.000 claims description 19
- 239000012298 atmosphere Substances 0.000 claims description 17
- 239000007789 gas Substances 0.000 claims description 16
- 239000004094 surface-active agent Substances 0.000 claims description 15
- 229910021645 metal ion Inorganic materials 0.000 claims description 14
- 239000002245 particle Substances 0.000 claims description 14
- 239000002082 metal nanoparticle Substances 0.000 claims description 12
- 230000001681 protective effect Effects 0.000 claims description 12
- 150000003839 salts Chemical class 0.000 claims description 12
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 claims description 11
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 10
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 10
- 229910052760 oxygen Inorganic materials 0.000 claims description 9
- 229920000428 triblock copolymer Polymers 0.000 claims description 9
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 7
- 125000004432 carbon atom Chemical group C* 0.000 claims description 7
- 239000001301 oxygen Substances 0.000 claims description 7
- 125000003172 aldehyde group Chemical group 0.000 claims description 6
- 150000001412 amines Chemical class 0.000 claims description 5
- 125000003277 amino group Chemical group 0.000 claims description 5
- 125000003118 aryl group Chemical group 0.000 claims description 5
- 239000001257 hydrogen Substances 0.000 claims description 5
- 229910052739 hydrogen Inorganic materials 0.000 claims description 5
- 229910052742 iron Inorganic materials 0.000 claims description 5
- 229910052759 nickel Inorganic materials 0.000 claims description 5
- 229910052763 palladium Inorganic materials 0.000 claims description 5
- 229910052697 platinum Inorganic materials 0.000 claims description 5
- 229910052703 rhodium Inorganic materials 0.000 claims description 5
- 229910052707 ruthenium Inorganic materials 0.000 claims description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 4
- 229910052802 copper Inorganic materials 0.000 claims description 4
- 125000005842 heteroatom Chemical group 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- 239000004215 Carbon black (E152) Substances 0.000 claims description 3
- 229920000463 Poly(ethylene glycol)-block-poly(propylene glycol)-block-poly(ethylene glycol) Polymers 0.000 claims description 3
- 239000011149 active material Substances 0.000 claims description 3
- 229930195733 hydrocarbon Natural products 0.000 claims description 3
- 230000001590 oxidative effect Effects 0.000 claims description 3
- 229920006395 saturated elastomer Polymers 0.000 claims description 3
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 2
- 125000002947 alkylene group Chemical group 0.000 claims description 2
- 229910052782 aluminium Inorganic materials 0.000 claims description 2
- 229910052804 chromium Inorganic materials 0.000 claims description 2
- 229910052735 hafnium Inorganic materials 0.000 claims description 2
- 150000002430 hydrocarbons Chemical class 0.000 claims description 2
- 229910052741 iridium Inorganic materials 0.000 claims description 2
- 229910052748 manganese Inorganic materials 0.000 claims description 2
- 229910052750 molybdenum Inorganic materials 0.000 claims description 2
- 229910052758 niobium Inorganic materials 0.000 claims description 2
- 229910052702 rhenium Inorganic materials 0.000 claims description 2
- 229910052711 selenium Inorganic materials 0.000 claims description 2
- 229910052717 sulfur Inorganic materials 0.000 claims description 2
- 229910052718 tin Inorganic materials 0.000 claims description 2
- 229910052719 titanium Inorganic materials 0.000 claims description 2
- 229910052721 tungsten Inorganic materials 0.000 claims description 2
- 229910052720 vanadium Inorganic materials 0.000 claims description 2
- 229910052727 yttrium Inorganic materials 0.000 claims description 2
- 229910052725 zinc Inorganic materials 0.000 claims description 2
- 229910052726 zirconium Inorganic materials 0.000 claims description 2
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 claims 3
- 125000003358 C2-C20 alkenyl group Chemical group 0.000 claims 1
- UBEWDCMIDFGDOO-UHFFFAOYSA-N cobalt(II,III) oxide Inorganic materials [O-2].[O-2].[O-2].[O-2].[Co+2].[Co+3].[Co+3] UBEWDCMIDFGDOO-UHFFFAOYSA-N 0.000 description 35
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 14
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 14
- XPFVYQJUAUNWIW-UHFFFAOYSA-N furfuryl alcohol Chemical compound OCC1=CC=CO1 XPFVYQJUAUNWIW-UHFFFAOYSA-N 0.000 description 13
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 12
- HYBBIBNJHNGZAN-UHFFFAOYSA-N Furaldehyde Natural products O=CC1=CC=CO1 HYBBIBNJHNGZAN-UHFFFAOYSA-N 0.000 description 12
- 230000015572 biosynthetic process Effects 0.000 description 12
- 239000011148 porous material Substances 0.000 description 12
- 238000006243 chemical reaction Methods 0.000 description 11
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 description 9
- 239000000243 solution Substances 0.000 description 9
- 238000003786 synthesis reaction Methods 0.000 description 9
- 238000009826 distribution Methods 0.000 description 8
- 230000000694 effects Effects 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 238000002441 X-ray diffraction Methods 0.000 description 7
- 229910052786 argon Inorganic materials 0.000 description 7
- 238000003917 TEM image Methods 0.000 description 6
- 230000003197 catalytic effect Effects 0.000 description 6
- 238000005342 ion exchange Methods 0.000 description 6
- 239000002923 metal particle Substances 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 229910001868 water Inorganic materials 0.000 description 6
- UIAFKZKHHVMJGS-UHFFFAOYSA-N 2,4-dihydroxybenzoic acid Chemical compound OC(=O)C1=CC=C(O)C=C1O UIAFKZKHHVMJGS-UHFFFAOYSA-N 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 5
- 238000010335 hydrothermal treatment Methods 0.000 description 5
- 229960004592 isopropanol Drugs 0.000 description 5
- 230000003647 oxidation Effects 0.000 description 5
- 238000007254 oxidation reaction Methods 0.000 description 5
- 238000001179 sorption measurement Methods 0.000 description 5
- DSLRVRBSNLHVBH-UHFFFAOYSA-N 2,5-furandimethanol Chemical compound OCC1=CC=C(CO)O1 DSLRVRBSNLHVBH-UHFFFAOYSA-N 0.000 description 4
- NOEGNKMFWQHSLB-UHFFFAOYSA-N 5-hydroxymethylfurfural Chemical compound OCC1=CC=C(C=O)O1 NOEGNKMFWQHSLB-UHFFFAOYSA-N 0.000 description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N Furan Chemical compound C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 4
- 239000004312 hexamethylene tetramine Substances 0.000 description 4
- 235000010299 hexamethylene tetramine Nutrition 0.000 description 4
- RJGBSYZFOCAGQY-UHFFFAOYSA-N hydroxymethylfurfural Natural products COC1=CC=C(C=O)O1 RJGBSYZFOCAGQY-UHFFFAOYSA-N 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 238000002429 nitrogen sorption measurement Methods 0.000 description 4
- 239000002243 precursor Substances 0.000 description 4
- 238000013341 scale-up Methods 0.000 description 4
- 239000010935 stainless steel Substances 0.000 description 4
- 229910001220 stainless steel Inorganic materials 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 238000000197 pyrolysis Methods 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- 238000001350 scanning transmission electron microscopy Methods 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- KJPRLNWUNMBNBZ-QPJJXVBHSA-N (E)-cinnamaldehyde Chemical compound O=C\C=C\C1=CC=CC=C1 KJPRLNWUNMBNBZ-QPJJXVBHSA-N 0.000 description 2
- NSQYDLCQAQCMGE-UHFFFAOYSA-N 2-butyl-4-hydroxy-5-methylfuran-3-one Chemical compound CCCCC1OC(C)=C(O)C1=O NSQYDLCQAQCMGE-UHFFFAOYSA-N 0.000 description 2
- 239000002028 Biomass Substances 0.000 description 2
- WTEVQBCEXWBHNA-UHFFFAOYSA-N Citral Natural products CC(C)=CCCC(C)=CC=O WTEVQBCEXWBHNA-UHFFFAOYSA-N 0.000 description 2
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 2
- 229920002415 Pluronic P-123 Polymers 0.000 description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 2
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 2
- 238000000026 X-ray photoelectron spectrum Methods 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 2
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 description 2
- 229940114055 beta-resorcylic acid Drugs 0.000 description 2
- 238000003763 carbonization Methods 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- 229940117916 cinnamic aldehyde Drugs 0.000 description 2
- KJPRLNWUNMBNBZ-UHFFFAOYSA-N cinnamic aldehyde Natural products O=CC=CC1=CC=CC=C1 KJPRLNWUNMBNBZ-UHFFFAOYSA-N 0.000 description 2
- 229940043350 citral Drugs 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- WTEVQBCEXWBHNA-JXMROGBWSA-N geranial Chemical compound CC(C)=CCC\C(C)=C\C=O WTEVQBCEXWBHNA-JXMROGBWSA-N 0.000 description 2
- 229910052734 helium Inorganic materials 0.000 description 2
- 239000001307 helium Substances 0.000 description 2
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 2
- 238000001027 hydrothermal synthesis Methods 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 238000004626 scanning electron microscopy Methods 0.000 description 2
- 238000001308 synthesis method Methods 0.000 description 2
- WXTMDXOMEHJXQO-UHFFFAOYSA-N 2,5-dihydroxybenzoic acid Chemical compound OC(=O)C1=CC(O)=CC=C1O WXTMDXOMEHJXQO-UHFFFAOYSA-N 0.000 description 1
- 229910018089 Al Ka Inorganic materials 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 239000004966 Carbon aerogel Substances 0.000 description 1
- 229910021094 Co(NO3)2-6H2O Inorganic materials 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910002483 Cu Ka Inorganic materials 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical group C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- 229920002488 Hemicellulose Polymers 0.000 description 1
- 229930040373 Paraformaldehyde Natural products 0.000 description 1
- 101710156645 Peptide deformylase 2 Proteins 0.000 description 1
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical group CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 1
- BCKXLBQYZLBQEK-KVVVOXFISA-M Sodium oleate Chemical compound [Na+].CCCCCCCC\C=C/CCCCCCCC([O-])=O BCKXLBQYZLBQEK-KVVVOXFISA-M 0.000 description 1
- IKHGUXGNUITLKF-XPULMUKRSA-N acetaldehyde Chemical compound [14CH]([14CH3])=O IKHGUXGNUITLKF-XPULMUKRSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 239000000908 ammonium hydroxide Substances 0.000 description 1
- 125000005428 anthryl group Chemical group [H]C1=C([H])C([H])=C2C([H])=C3C(*)=C([H])C([H])=C([H])C3=C([H])C2=C1[H] 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000012300 argon atmosphere Substances 0.000 description 1
- 150000003934 aromatic aldehydes Chemical class 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 230000002860 competitive effect Effects 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- MLUCVPSAIODCQM-NSCUHMNNSA-N crotonaldehyde Chemical compound C\C=C\C=O MLUCVPSAIODCQM-NSCUHMNNSA-N 0.000 description 1
- MLUCVPSAIODCQM-UHFFFAOYSA-N crotonaldehyde Natural products CC=CC=O MLUCVPSAIODCQM-UHFFFAOYSA-N 0.000 description 1
- 150000003983 crown ethers Chemical class 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 208000001848 dysentery Diseases 0.000 description 1
- 238000000921 elemental analysis Methods 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 150000002240 furans Chemical class 0.000 description 1
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- SYECJBOWSGTPLU-UHFFFAOYSA-N hexane-1,1-diamine Chemical compound CCCCCC(N)N SYECJBOWSGTPLU-UHFFFAOYSA-N 0.000 description 1
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 238000007327 hydrogenolysis reaction Methods 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 125000005647 linker group Chemical group 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 238000003760 magnetic stirring Methods 0.000 description 1
- 229910001092 metal group alloy Inorganic materials 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 229910052756 noble gas Inorganic materials 0.000 description 1
- 230000036963 noncompetitive effect Effects 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 description 1
- 229920002866 paraformaldehyde Polymers 0.000 description 1
- 238000005325 percolation Methods 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229920001983 poloxamer Polymers 0.000 description 1
- 238000000634 powder X-ray diffraction Methods 0.000 description 1
- AOHJOMMDDJHIJH-UHFFFAOYSA-N propylenediamine Chemical compound CC(N)CN AOHJOMMDDJHIJH-UHFFFAOYSA-N 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 238000000851 scanning transmission electron micrograph Methods 0.000 description 1
- 150000003333 secondary alcohols Chemical class 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000012265 solid product Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000004627 transmission electron microscopy Methods 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
- B01J37/084—Decomposition of carbon-containing compounds into carbon
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/18—Carbon
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/75—Cobalt
-
- B01J35/30—
-
- B01J35/393—
-
- B01J35/399—
-
- B01J35/647—
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
- B01J37/086—Decomposition of an organometallic compound, a metal complex or a metal salt of a carboxylic acid
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/12—Oxidising
- B01J37/14—Oxidising with gases containing free oxygen
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/16—Reducing
- B01J37/18—Reducing with gases containing free hydrogen
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/30—Ion-exchange
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/05—Preparation or purification of carbon not covered by groups C01B32/15, C01B32/20, C01B32/25, C01B32/30
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/132—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group
- C07C29/136—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH
- C07C29/14—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of a —CHO group
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
- C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
- C07D307/34—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
- C07D307/38—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with substituted hydrocarbon radicals attached to ring carbon atoms
- C07D307/40—Radicals substituted by oxygen atoms
- C07D307/42—Singly bound oxygen atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
- C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
- C07D307/34—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
- C07D307/38—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with substituted hydrocarbon radicals attached to ring carbon atoms
- C07D307/40—Radicals substituted by oxygen atoms
- C07D307/42—Singly bound oxygen atoms
- C07D307/44—Furfuryl alcohol
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G14/00—Condensation polymers of aldehydes or ketones with two or more other monomers covered by at least two of the groups C08G8/00 - C08G12/00
- C08G14/02—Condensation polymers of aldehydes or ketones with two or more other monomers covered by at least two of the groups C08G8/00 - C08G12/00 of aldehydes
- C08G14/04—Condensation polymers of aldehydes or ketones with two or more other monomers covered by at least two of the groups C08G8/00 - C08G12/00 of aldehydes with phenols
- C08G14/06—Condensation polymers of aldehydes or ketones with two or more other monomers covered by at least two of the groups C08G8/00 - C08G12/00 of aldehydes with phenols and monomers containing hydrogen attached to nitrogen
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J33/00—Protection of catalysts, e.g. by coating
-
- B01J35/617—
-
- B01J35/635—
-
- B01J35/67—
Definitions
- the present invention refers to a process for preparing mesoporous carbon (MC) loaded with catalytically active metal and/or metal oxide nanoparticles, the so- obtained MC loaded with metal oxide nanoparticles and the use thereof as a catalyst in a transfer hydrogenation process of ⁇ , ⁇ -unsaturated aldehydes to unsaturated alcohols.
- the present invention also refers to a transfer hydrogenation process of a, ⁇ -un saturated aldehydes to unsaturated alcohols catalyzed by metal and/or metal oxide nanoparticles, in particular by Co3O 4 nanoparticles supported on MC.
- FAL furfural
- HMF 5-hydroxymethylfurfural
- selective hydrogenation of FAL to furfuryl alcohol (FOL) and HMF to 2,5-bis-(hydroxymethyl)furan (BHMF) has great potential for industrial applications, because FOL and BHMF can be used as precursors in synthesis of polymers, resins and adhesives, and as intermediates in generation of drugs and crown ethers.
- the catalysts must be highly active and selective towards unsaturated alcohols in a simple catalytic system, which is also controllable and scalable.
- Porous carbon structures on the basis of carbon aerogels and being loaded with catalytically active metal nanoparticles and/or metal oxide nanoparticles are known from ChemElectroChem 2015, pages 2079-2088.
- the carbon structures are microporous to mesoporous having very small pores of 2 nm to 4 nm and thus pores having a restricted access only.
- a clear teaching to obtain larger mesoporous structures only is not given in said reference.
- the inventors of the present invention have developed a process in which a mesostructured polymer gel is firstly synthesized using 2,4-dihydroxybenzoic acid (DA) and hexamethylenetetramine (HMT) as polymer precursors and a triblock copolymer such as P123 as surfactant without the addition of a fatty acid salt such as sodium oleate under hydrothermal process conditions (such as at 130 °C for 4 h), and secondly, introducing the Co 2+ ions homogenously into the mesostructured polymer gel framework in the ion-exchanging step, and thirdly, treating the so- obtained polymer gel loaded with Co 2+ ions at an elevated temperature for reduction (500 °C, 10% H 2 in argon) first, and then mild oxidation (room temperature, 1 % O 2 in argon) so that Co 3 O 4 nanoparticles supported on MC (Co3O 4 /MC) are formed after ( Figure 1 ).
- DA 2,4-dihydroxy
- XRD pattern shows the typical reflections corresponding to the Co 3 O crystals (PDF-2 entry 43-1003), indicating the formation of Co3O 4 nanoparticles after the reduction and mild oxidation processes (Figure 2g).
- XPS spectrum further confirms the formation of Co3O 4 nanoparticles ( Figure 2h).
- AAS analysis Atomic absorption spectrometer, Perkin Elmer AAnalyst 200
- the Co fraction in Co 3 O /MC is 15 wt%, corresponding to a Co3O 4 fraction of 20 wt%.
- N 2 sorption isotherm of Co3O 4 MC shows a type-IV curve that is characteristic of mesoporous structure ( Figure 2i).
- the sorption increase in the high relative pressure region indicates the existence of macropores, which is consistent with the SEM observation.
- the surface area and pore size distribution of Co3O 4 MC are 642 m 2 g "1 and 1 1 nm, respectively. Without introducing Co species, MC with surface area of 722 m 2 g "1 and pore size of -9.5 nm is generated directly after carbonization at 800 °C in argon ( Figure 3). This material is a good candidate as catalyst support or adsorbent. Using traditional impregnation methods, the metal particle size distribution is always broad, which leads to the inefficient use of the Co species because of the size-dependent activity of Co3O 4 .
- the present synthesis method is suitable to generate Co3O 4 nanoparticles with narrow size distribution in the range from 2 to 5 nm, preferably 2 to 4 nm, in particular 2.5 to 3.5 nm ( ⁇ 3 nm) and disperse them in a mesoporous framework of MC homogeneously, which realizes the highly efficient utilization of Co species.
- the invention is therefore directed to a process for preparing a mesoporous carbon structure (MC) loaded with catalytically active metal nanoparticles and/or metal oxide nanoparticles, comprising the following steps:
- the aromatic compound is linked with the aldehyde in the presence of the amine and a mesostructured polymer gel is obtained.
- the obtained polymer gel is then loaded with metal ions which may finally be present as metal particles and/or metal oxide particles, depending on the metal.
- the protective gas atmosphere serves for a carbonization of the polymer gel into the desired mesoporous carbon structure and the oxygen content should be as low in order not to allow an oxidation of said MC structure.
- a noble metal will be present as metal particles whereas non-noble metals will be present as a metal which might optionally be further oxidized to a corresponding metal oxide and which may be obtainable by treating the obtained mesoporous carbon structure in a gas atmosphere with an oxygen content under conditions under the MC support is not oxidized, preferably in a temperature range from 20 °C to 200 °C, more preferred at a temperature between 20 °C and 100 °C whereby a mesoporous carbon network structure loaded with catalytically active metal and/or metal oxide nanoparticles is obtained.
- the mesoporous carbon structure loaded with catalytically active metal and/or metal oxide nanoparticles may be obtained by reacting an aromatic compound having at least one -COOH group and having at least one hydroxyl group with an aldehyde in presence of an aliphatic amine, said amine having 2 to 12 carbon atoms and at least two amine groups, and an amphiphilic triblock copolymer surfactant under hydrothermal conditions in molar ratios of 1 to 3 (aromatic compound) to 1 to 5 (of reacting aldehyde group) in the presence of the aliphatic amine (0.5 to 1 .5) and surfactant (0.03 to 0.09), whereby a mesostructured polymer gel is obtained,
- the aromatic compound having at least one -COOH group and having at least one hydroxyl group may be selected from aromatic hydrocarbons such as phenyl, naphthyl, or anthryl, and can be, as example, dihydroxy benzoic acid.
- the aromatic compound may preferably have up to three -COOH groups and up to three hydroxyl groups whereby an aromatic compound having three or four functional groups, with at least one -COOH group and at least one hydroxyl group and the other(s) being selected from -COOH and hydroxyl, is preferred.
- the aromatic compound is used in an amount of 2 wt% to 20 wt% based on the weight of the solvent.
- the aldehyde may be selected from an aliphatic Ci to C 12 hydrocarbon aldehyde such as formaldehyde, paraformaldehyde, furfuraldehyde, acetaldehyde, crotonaldehyde, an aromatic aldehyde such as benzaldehyde or substituted derivatives thereof or a compound which can be decomposed into formaldehyde such as hexamethylenetetramine and urea.
- aldehyde compound is intended to indicate one -CHO-unit used for bridging the aromatic compound.
- the aliphatic amine serves as a linker between the -COOH group of two aromatic compounds or as base to neutralize the acidity of the aromatic compound with - COOH group and may be any aliphatic hydrocarbon having 2 to 12 carbon atoms and having at least two, three or four amino groups. Examples are ethylene diamine, propylene diamine, hexane diamine, octane triamine, or mixtures of different aliphatic amines.
- the aliphatic amine is soluble in or miscible with water.
- an amphiphilic triblock copolymer such as a poly(ethylene oxide)- poly(alkylene oxide)-poly(ethylene oxide) polymer, exemplarily a poly(ethylene oxide)-poly(propylene oxide)-poly(ethylene oxide) polymer, e.g. Pluronic polymers having a general structure of 2 to 130 terminal ethylene oxide units on either side of the polymer and 15 to 67 central propylene oxide units, is used in the inventive process.
- the central alkylene oxide moiety has at least three carbon atoms.
- amphiphilic triblock copolymer of poly(ethylene oxide)-poly(propylene oxide)- poly(ethylene oxide) are most preferred.
- said amphiphilic triblock copolymers are used as the only surfactant and no further surface-active materials are added in the hydrothermal treatment.
- the hydrothermal treatment is generally carried out in an aqueous solution at a temperature in the range of 60 °C or more up to 200 °C, preferably from about 80 °C to 200 °C, for an usual reaction time in the range of 0.5 to 48 hours, preferably under autogenous pressure in an autoclave which pressure is usually in the range of 1 bar to 20 bar.
- the aromatic compound having at least one -COOH group and having at least one hydroxyl group is reacted with the aldehyde compound in a kind of phenol-aldehyde resin formation process in the presence of the amphiphilic triblock copolymer as surfactant, thus leading to the mesostructured polymer gel which is then optionally comminuted or grinded and optionally washed, preferably with water, and then treated with the metal salt.
- the mesostructured polymer gel is converted, in a protective gas atmosphere at an elevated temperature, to the MC loaded with metal and/or metal oxide particles.
- the aromatic compound having at least one - COOH group and having at least one hydroxyl group is preferably polymerized with the aldehyde or the aldehyde (precursor) compound producing the aldehyde group in molar ratios of 1 to 3 (aromatic compound) to 1 to 5 (of reacting aldehyde group) in the presence of the aliphatic amine (0.5 to 1 .5) and surfactant (0.03 to 0.09).
- the compounds as indicated before are used in a ratio of 2 : 3: 1 : 0.06.
- the compound producing the -CHO group can be preferably used in over-stoichiometric amounts in order to ensure complete crosslinking of the aromatic molecules. If needed, the pH of the reaction mixture in the hydrothermal treatment is adjusted to a weakly basic range from 7 to 12.
- the obtained mesostructured polymer gel is treated with a solution of a metal salt whereby a mesostructured polymer gel loaded with metal ions is obtained.
- the ions attached to the polymer commonly H + or NH +
- the pH of the solution may be adjusted to 7 to 12 by adding a base such as ammonia.
- the temperature in the ion-exchanging step may be about 25°C to 100°C, the reaction time may be about 0.5 to 48 hours.
- any metal is suitable and is selected from Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Al, Mo, Se, Sn, Pt, Ru, Rh, Zr, Hf, Re, Pd, W, Ir, Os, Rh, Nb, Ta, Pb, Bi, Au, Ag, Sc, Y and preferably from Fe, Co, Ni, Pt, Ru, Rh and Pd. Co is most preferred.
- the metal may be applied in the form of a salt and mixtures thereof, preferably in the form of a solution of a metal salt or a mixture thereof, which are later in the process converted to the metal, metal alloy or metal oxides, depending on the used metal.
- the metal may be used in an amount to provide a metal load of 0,1 wt% up to 30 wt.%, preferably 3 to 20 wt%, more preferred 5 to 15 wt.% referred to the final product.
- the obtained polymer gel loaded with metal ions is treated in a protective gas atmosphere, preferably at an elevated temperature in the range of 400 °C to 1000 °C whereby a mesoporous carbon (MC) structure loaded with metal particles and/or metal oxide particles is obtained.
- a protective gas atmosphere is to be generally understood as an atmosphere which does not allow the oxidation of the MC support and may comprise a noble gas such as argon, helium, or an inert gas such as nitrogen or mixtures thereof, and hydrogen, which is preferably used in a volume ratio of 1 to 10 % hydrogen of the gas atmosphere. By means of the hydrogen content, the reduction of metal ions to metal particles can be supported.
- the obtained mesoporous carbon structure is treated in a gas atmosphere with an oxygen content under conditions which are not oxidizing the MC support, preferably in a temperature range from 20 °C to 200 °C, more preferred at a temperature between 20 °C and 100 °C whereby a mesoporous carbon network structure loaded with catalytically active metal and/or metal oxide nanoparticles is obtained.
- the treatment may be carried out in an atmosphere comprising protective gas and oxygen at temperature ranging from 20 °C to 200 °C for 5 min to 12 h, wherein the protective gas comprises nitrogen, helium, argon, or any mixture thereof and wherein the volume percentage of oxygen is about 0.1 to 10.
- the present invention also refers to the mesoporous carbon loaded with metal oxide nanoparticles, obtainable according to the process of the present invention, in particular to the mesoporous carbon loaded with metal oxide nanoparticles, wherein the metal oxide nanoparticles have a particle size' in the range of 1 to 10 nm, preferably 2 to 6 nm, in particular 2.5 to 4.5 nm, for Co 3 O 4 in particular from 2 to 5 nm, preferred 2 to 4 nm and most preferred from 2.5 to 3.5 nm, all measured from the TEM images and also calculated from the XRD data.
- the surface area, pore volume, pore size and the size of Co particles are superior.
- the surface area is ⁇ 500 m 2 /g
- the Co oxide size is ranging from 5 to 40 nm
- pore size is ranging from 2 to 4 nm.
- the surface area is ranging from 500 to 1000 m 2 /g (BET)
- the pore size is centered at 6 to 15 nm
- the Co 3 O 4 diameter is 2 to 5 nm.
- the diameters of the metal oxide particles were measured from the TEM image and correspond to the ones which are calculated based on XRD data.
- the present invention refers to a mesoporous carbon structure/particles loaded with metal nanoparticles and/or metal oxide nanoparticles, obtainable according to the inventive processes, wherein the specific surface area is 500 m 2 /g to 1000 m 2 /g, the mesopore size is centered at 6 to 15 nm, preferably 9 to 12 nm according to the nitrogen sorption measurement, the metal loading amount is ranging from 0.1 to 30 wt% referred to the total weight of the loaded MC support; and the particle size (diameter of the metal particles) is ranging from 1 to 10 nm.
- Said mesoporous carbon supported Co 3 O 4 nanoparticles can be preferably used as a catalyst, in particular as a catalytically active material in a process for transfer hydrogenation of a, ⁇ -un saturated aldehydes in the presence of the inventive catalyst and a H-donor, for example a secondary alcohol such as iso-propanol, to unsaturated alcohols as represented in the following scheme:
- Figure 1 shows a schematic representation of the inventive process
- Figure 2 shows a,b) TEM images (inset in Figure b shows the Co3O 4 particle size distribution), c) SEM image, d-f) STEM, g) XRD pattern, h) XPS spectrum, and i) N 2 sorption isotherm of Co 3 O /MC (inset in Figure i shows the pore size distribution);
- Figure 3 shows the structural characterization of mesoporous carbon pyrolysis at 800 °C: a, b) TEM images, and c, d) N 2 isotherm and pore size distribution;
- Figure 4 shows TEM images and XRD patterns of Co3O 4 materials: a, b) Co3O 4 - nanocasting, c, d) Co 3 O 4 -6 nm, and e, f) Co 3 O 4 -17 nm;
- Figure 5 shows a) catalytic performances for the transfer hydrogenation of cinnamaldehyde and citral over Co3O 4 MC, b) the recycling results for transfer hydrogenation of FAL over Co3O 4 MC.
- Figure 6 shows a,b) TEM images of Co 3 O /MC after 6 runs, c) XRD patterns and d) N 2 isotherms of Co3O 4 MC before and after 6 runs.
- the polymer product was re-dispersed in 120 ml_ of solution (96 ml_ of H 2 O and 24 ml_ of ammonium hydroxide solution (28.0- 30.0%)) containing 4.62 mmol (1 .345 g) of Co(NO 3 ) 2 -6H 2 O, stirred at 50 °C for 6 h. Then, the product was collected by filtration, washed three times with deionized water and dried at 50 °C under vacuum for 8 h. Finally, ⁇ 1 .64 g of Co3O 4 MC was obtained by pyrolysis under H 2 /Ar (5%/95%) atmosphere.
- the pyrolysis procedure used here was as follows: the sample was heated to 400 °C with a rate of 2 °C min "1 and kept at that temperature for 3 h, then heated to 500 °C with a rate of 1 °C min "1 and kept at that temperature for 2 h. Afterwards, the sample was allowed to cool to room temperature and passivate in a flow of 1 % oxygen in argon for 2 h. For synthesis of MC without the metal load, the polymer gel product was directly carbonized by heating up to 800 °C with a heating rate of 2 °C min "1 and holding at that temperature for 3 h under argon atmosphere.
- Co3O 4 -6 nm and Co3O 4 -17 nm were synthesized via a hydrothermal approach according to literature 1
- 0.5 g of Co(CH 3 COO)2-4H 2 O was first dissolved in 25 mL of ethanol. Then 2.5 mL of 25% ammonia was added under vigorous stirring. After 10 min the obtained slurry was transferred to a teflon-lined stainless steel autoclave of 45 mL capacity, sealed and maintained at 150 ° C for 3 h.
- TEM Transmission electron microscopy
- STEM scanning transmission electron microscopy
- SEM scanning electron microscopy
- Powder X-ray diffraction was performed on a Stoe STADI P diffractometer operating in reflection mode with Cu Ka radiation using a secondary graphite monochromator.
- Nitrogen sorption isotherms were measured with a Micromeritics ASAP 2010 adsorption analyzer at 77 K. Prior to the measurements, the sample was degassed at a temperature of 250 °C for 6 h.
- the specific surface areas were calculated from the adsorption data in the relative pressure range of 0.05 to 0.3 using the Brunauer-Emmett-Teller (BET) method. Pore size distributions were determined with the Barrett-Joyner-Halenda (BJH) method from the adsorption branch (desorption data which are normally recommended, can be influenced by network percolation or cavitation effects). The total pore volume was estimated from the amount adsorbed at a relative pressure of 0.97.
- BET Brunauer-Emmett-Teller
- X-ray photoelectron spectroscopy (XPS) measurements were carried out with a Kratos HSi spectrometer with a hemispherical analyzer.
- An analyzer pass energy of 40 eV was applied for the narrow scans.
- Hybrid mode was used as lens mode.
- the base pressure during the experiment in the analysis chamber was 4x10 "7 Pa. To account for charging effects of carbonized samples, the binding energy values were referred to C 1 s at 284.5 eV.
- Elemental analysis was carried out at Mikrolab Kolbe (Hohenweg 17, D-45470, Mulheim an der Ruhr) by AAnalyst 200 Atomic Absorption Spectrometer (AAS).
- the inventors have developed a simple and scalable method, including steps of hydrothermal process, ion-exchanging and reducing/mild oxidizing, to synthesize metal oxide nanoparticles such as Co3O 4 nanoparticles supported in the framework of the mesoporous carbon network.
- metal oxide nanoparticles such as Co3O 4 nanoparticles supported in the framework of the mesoporous carbon network.
- the Co3O 4 nanoparticles with a diameter of ⁇ 3 nm were finely dispersed in the framework of MC after reduction and mild oxidation processes.
- the as-obtained Co3O 4 MC is more efficient than Co3O 4 -nanocasting, Co 3 O -6 nm and Co 3 O -17 nm ( Figure 4) as catalyst for the transfer hydrogenation of ⁇ , ⁇ -unsaturated aldehydes (Table 1 , Figure 5a).
- the selectivities towards unsaturated alcohols over Co3O 4 MC are always higher than 97% at full conversion.
- the catalyst after reaction was filtrated and washed with 2-propanol, followed by drying and treating under H 2 /Ar at 300 °C for 2 h to remove residues from the surface of the used Co3O 4 MC.
- the Co3O 4 MC catalyst was recycled at least six times without loss of activity, indicating a high stability of Co3O 4 MC under the reaction conditions ( Figure 5b, 6).
- the gram-scale preparation of furfural alcohol over Co3O 4 MC indicates that such catalytic system is scalable without pressure issue (Table 1 , entry 13).
- the as- obtained furfuryl alcohol can be used as polymer precursor directly without further purification to synthesize ordered mesoporous carbon (CMK-5). Therefore, the present catalytic system for transfer hydrogenation of ⁇ , ⁇ - unsaturated aldehydes over Co 3 O /MC has the potential to be utilized in industry.
- the synthesis methodology of Co3O 4 MC which is also easy to scale up, may be further extended to design other metal or metal oxide catalysts supported on MC.
Abstract
The present invention refers to a process for preparing mesoporous carbon loaded with a catalytically active metal and/or metal oxide nanoparticles, the so-obtained mesoporous carbon and the use thereof as a catalyst in a transfer hydrogenation process of α,β-unsaturated aldehydes to unsaturated alcohols.
Description
PREPARATION OF MESOPOROUS CARBON WITH CATALYTICALLY ACTIVE METAL OXIDE NANOPARTICLES FOR THE SELECTIVE HYDROGENATION OF ALPHA-BETA-UNSATURATED ALDEHYDES
The present invention refers to a process for preparing mesoporous carbon (MC) loaded with catalytically active metal and/or metal oxide nanoparticles, the so- obtained MC loaded with metal oxide nanoparticles and the use thereof as a catalyst in a transfer hydrogenation process of α,β-unsaturated aldehydes to unsaturated alcohols. Thus, the present invention also refers to a transfer hydrogenation process of a, β-un saturated aldehydes to unsaturated alcohols catalyzed by metal and/or metal oxide nanoparticles, in particular by Co3O4 nanoparticles supported on MC.
The production of high value-added chemicals from biomass is of a major interest to reduce dependence of petroleum-based chemicals. Furan derivatives of furfural (FAL) and 5-hydroxymethylfurfural (HMF), which can be produced from hemicellulose and cellulose respectively, are considered as promising platform molecules to bridge the gap between biomass resources and bio-chemicals since they can be converted into a variety of high value-added chemicals and fuels. Particularly, selective hydrogenation of FAL to furfuryl alcohol (FOL) and HMF to 2,5-bis-(hydroxymethyl)furan (BHMF) has great potential for industrial applications, because FOL and BHMF can be used as precursors in synthesis of polymers, resins and adhesives, and as intermediates in generation of drugs and crown ethers.
However, due to the different functionalities of furan-based α,β-unsaturated aldehydes (e.g., furan ring, C=C and C=O groups), only selective hydrogenation of C=O bond is challenging. Many byproducts were often formed by hydrogenolysis of the -CH=O side chain to -CH3, or hydrogenation of the furan ring and its opening, leading to low yield of the desired unsaturated alcohols and increasing cost of product purification.
In general, conventional hydrogenation catalysts based on noble or metals (e.g., Pd, Pt, Ru, Rh, Cu, or Ni) show high activity but poor selectivity toward unsaturated alcohols. In order to enhance the selectivity for unsaturated alcohols over such catalysts, additives, stabilizers/ligands, second metal components or functional supports were introduced into the catalytic system or catalysts. In some cases high selectivity toward unsaturated alcohols and high activity were indeed achieved using above methods. However, due to the complexity of reaction mechanism (e.g., competitive/non-competitive, dissociative/non-dissociative adsorption, side reaction), selectivities and activities in these cases can be affected by a series of factors, including the structure/component of catalysts (e.g., particle size, shape, molar ratio of different components) and the reaction conditions (e.g., temperature, pressure and solvents). In other words, dramatic decrease of selectivity and/or activity often occurs because it is very difficult to control these factors precisely, especially in large scale applications.
Therefore, it is necessary to develop a simple method for scale-up of catalyst synthesis; the catalysts must be highly active and selective towards unsaturated alcohols in a simple catalytic system, which is also controllable and scalable. Thus, the design of suitable catalyst and/or catalytic system that facilitate selective hydrogenation of C=O bond in the presence of other functionalities is highly desirable.
Porous carbon structures on the basis of carbon aerogels and being loaded with catalytically active metal nanoparticles and/or metal oxide nanoparticles are known from ChemElectroChem 2015, pages 2079-2088. However, the carbon structures are microporous to mesoporous having very small pores of 2 nm to 4 nm and thus pores having a restricted access only. A clear teaching to obtain larger mesoporous structures only is not given in said reference. The inventors of the present invention have developed a process in which a mesostructured polymer gel is firstly synthesized using 2,4-dihydroxybenzoic acid (DA) and hexamethylenetetramine (HMT) as polymer precursors and a triblock copolymer such as P123 as surfactant without the addition of a fatty acid salt such
as sodium oleate under hydrothermal process conditions (such as at 130 °C for 4 h), and secondly, introducing the Co2+ ions homogenously into the mesostructured polymer gel framework in the ion-exchanging step, and thirdly, treating the so- obtained polymer gel loaded with Co2+ ions at an elevated temperature for reduction (500 °C, 10% H2 in argon) first, and then mild oxidation (room temperature, 1 % O2 in argon) so that Co3O4 nanoparticles supported on MC (Co3O4/MC) are formed after (Figure 1 ). Said synthetic processes are easy to scale up. The inventors found out that, in case of Co3O /MC, the MC support is highly mesoporous and the Co3O4 nanoparticles with a diameter of ~3 nm are finely dispersed in the mesoporous framework of MC (Figure 2a, b). Many macropores are also observed in SEM images (Figure 2c), which may be generated from the polymer gel structure. STEM images further confirm that the Co3O nanoparticles are dispersed very well in the framework of MC with narrow particle size distribution (Figure 2d-f). Most importantly, no bigger Co3O4 particles are formed using the present synthesis method. XRD pattern shows the typical reflections corresponding to the Co3O crystals (PDF-2 entry 43-1003), indicating the formation of Co3O4 nanoparticles after the reduction and mild oxidation processes (Figure 2g). XPS spectrum further confirms the formation of Co3O4 nanoparticles (Figure 2h). Based on AAS analysis (Atomic absorption spectrometer, Perkin Elmer AAnalyst 200), the Co fraction in Co3O /MC is 15 wt%, corresponding to a Co3O4 fraction of 20 wt%. N2 sorption isotherm of Co3O4 MC shows a type-IV curve that is characteristic of mesoporous structure (Figure 2i). In addition, the sorption increase in the high relative pressure region (p/p0>0.9) indicates the existence of macropores, which is consistent with the SEM observation. The surface area and pore size distribution of Co3O4 MC are 642 m2 g"1 and 1 1 nm, respectively. Without introducing Co species, MC with surface area of 722 m2 g"1 and pore size of -9.5 nm is generated directly after carbonization at 800 °C in argon (Figure 3). This material is a good candidate as catalyst support or adsorbent.
Using traditional impregnation methods, the metal particle size distribution is always broad, which leads to the inefficient use of the Co species because of the size-dependent activity of Co3O4. The present synthesis method is suitable to generate Co3O4 nanoparticles with narrow size distribution in the range from 2 to 5 nm, preferably 2 to 4 nm, in particular 2.5 to 3.5 nm (~3 nm) and disperse them in a mesoporous framework of MC homogeneously, which realizes the highly efficient utilization of Co species.
The invention is therefore directed to a process for preparing a mesoporous carbon structure (MC) loaded with catalytically active metal nanoparticles and/or metal oxide nanoparticles, comprising the following steps:
reacting an aromatic compound having at least one -COOH group and having at least one hydroxyl group with an aldehyde or compound in the presence of an aliphatic amine, said amine having 2 to 12 carbon atoms and at least two amine groups, and an amphiphilic triblock copolymer surfactant under hydrothermal conditions in molar ratios of 1 to 3 (aromatic compound) to 1 to 5 (of reacting aldehyde group) in the presence of the aliphatic amine (0.5 to 1 .5) and surfactant (0.03 to 0.09), whereby a mesostructured polymer gel is obtained,
treating the obtained mesostructured polymer gel with a solution of a metal salt or with a mixture of different salts which is simply an ion-exchanging step whereby a mesostructured polymer gel loaded with metal ions is obtained, treating the obtained polymer gel loaded with metal ions in a protective gas atmosphere at an elevated temperature in the range of 400 °C to 1000 °C whereby a mesoporous carbon structure loaded with catalytically active metal nanoparticles and/or metal oxide nanoparticles is obtained.
In the process, the aromatic compound is linked with the aldehyde in the presence of the amine and a mesostructured polymer gel is obtained. The obtained polymer gel is then loaded with metal ions which may finally be present as metal particles and/or metal oxide particles, depending on the metal. The protective gas atmosphere serves for a carbonization of the polymer gel into the desired mesoporous carbon structure and the oxygen content should be as low in order
not to allow an oxidation of said MC structure. Depending on the reaction conditions, a noble metal will be present as metal particles whereas non-noble metals will be present as a metal which might optionally be further oxidized to a corresponding metal oxide and which may be obtainable by treating the obtained mesoporous carbon structure in a gas atmosphere with an oxygen content under conditions under the MC support is not oxidized, preferably in a temperature range from 20 °C to 200 °C, more preferred at a temperature between 20 °C and 100 °C whereby a mesoporous carbon network structure loaded with catalytically active metal and/or metal oxide nanoparticles is obtained.
As an alternative process, the mesoporous carbon structure loaded with catalytically active metal and/or metal oxide nanoparticles may be obtained by reacting an aromatic compound having at least one -COOH group and having at least one hydroxyl group with an aldehyde in presence of an aliphatic amine, said amine having 2 to 12 carbon atoms and at least two amine groups, and an amphiphilic triblock copolymer surfactant under hydrothermal conditions in molar ratios of 1 to 3 (aromatic compound) to 1 to 5 (of reacting aldehyde group) in the presence of the aliphatic amine (0.5 to 1 .5) and surfactant (0.03 to 0.09), whereby a mesostructured polymer gel is obtained,
treating the obtained polymer gel in a protective gas atmosphere at an elevated temperature in the range of 400 °C to 1000 °C, whereby a mesoporous carbon structure is obtained,
impregnating the obtained mesoporous carbon structure with a solution of a metal salt or with a mixture of different salts whereby a mesoporous carbon structure loaded with metal ions is obtained;
treating the obtained mesoporous carbon structure loaded with metal ions in a protective gas atmosphere at an elevated temperature in the range of 200 °C to 1000 °C, optionally in the presence of hydrogen whereby a mesoporous carbon structure loaded with catalytically active metal nanoparticles and/or metal oxide nanoparticles is obtained.
In the latter process, an empty mesoporous structure is prepared first, and in a further step loaded with the metal ions which are then converted to the metal and/or metal oxide particles. In the inventive process, the aromatic compound having at least one -COOH group and having at least one hydroxyl group may be selected from aromatic hydrocarbons such as phenyl, naphthyl, or anthryl, and can be, as example, dihydroxy benzoic acid. The aromatic compound may preferably have up to three -COOH groups and up to three hydroxyl groups whereby an aromatic compound having three or four functional groups, with at least one -COOH group and at least one hydroxyl group and the other(s) being selected from -COOH and hydroxyl, is preferred. Preferably, the aromatic compound is used in an amount of 2 wt% to 20 wt% based on the weight of the solvent. The aldehyde may be selected from an aliphatic Ci to C12 hydrocarbon aldehyde such as formaldehyde, paraformaldehyde, furfuraldehyde, acetaldehyde, crotonaldehyde, an aromatic aldehyde such as benzaldehyde or substituted derivatives thereof or a compound which can be decomposed into formaldehyde such as hexamethylenetetramine and urea. The expression "aldehyde compound" is intended to indicate one -CHO-unit used for bridging the aromatic compound.
The aliphatic amine serves as a linker between the -COOH group of two aromatic compounds or as base to neutralize the acidity of the aromatic compound with - COOH group and may be any aliphatic hydrocarbon having 2 to 12 carbon atoms and having at least two, three or four amino groups. Examples are ethylene diamine, propylene diamine, hexane diamine, octane triamine, or mixtures of different aliphatic amines. Preferably, the aliphatic amine is soluble in or miscible with water. As surfactant, an amphiphilic triblock copolymer such as a poly(ethylene oxide)- poly(alkylene oxide)-poly(ethylene oxide) polymer, exemplarily a poly(ethylene oxide)-poly(propylene oxide)-poly(ethylene oxide) polymer, e.g. Pluronic polymers having a general structure of 2 to 130 terminal ethylene oxide units on either side
of the polymer and 15 to 67 central propylene oxide units, is used in the inventive process. The central alkylene oxide moiety has at least three carbon atoms. Thus, amphiphilic triblock copolymer of poly(ethylene oxide)-poly(propylene oxide)- poly(ethylene oxide) are most preferred. Preferably, said amphiphilic triblock copolymers are used as the only surfactant and no further surface-active materials are added in the hydrothermal treatment.
The hydrothermal treatment is generally carried out in an aqueous solution at a temperature in the range of 60 °C or more up to 200 °C, preferably from about 80 °C to 200 °C, for an usual reaction time in the range of 0.5 to 48 hours, preferably under autogenous pressure in an autoclave which pressure is usually in the range of 1 bar to 20 bar.
During the hydrothermal treatment, the aromatic compound having at least one -COOH group and having at least one hydroxyl group is reacted with the aldehyde compound in a kind of phenol-aldehyde resin formation process in the presence of the amphiphilic triblock copolymer as surfactant, thus leading to the mesostructured polymer gel which is then optionally comminuted or grinded and optionally washed, preferably with water, and then treated with the metal salt. In the next process step, the mesostructured polymer gel is converted, in a protective gas atmosphere at an elevated temperature, to the MC loaded with metal and/or metal oxide particles.
In the hydrothermal treatment step, the aromatic compound having at least one - COOH group and having at least one hydroxyl group is preferably polymerized with the aldehyde or the aldehyde (precursor) compound producing the aldehyde group in molar ratios of 1 to 3 (aromatic compound) to 1 to 5 (of reacting aldehyde group) in the presence of the aliphatic amine (0.5 to 1 .5) and surfactant (0.03 to 0.09). In a very simple ratio, the compounds as indicated before are used in a ratio of 2 : 3: 1 : 0.06. In a particular embodiment, the compound producing the -CHO group can be preferably used in over-stoichiometric amounts in order to ensure complete crosslinking of the aromatic molecules.
If needed, the pH of the reaction mixture in the hydrothermal treatment is adjusted to a weakly basic range from 7 to 12.
In the next step, the obtained mesostructured polymer gel is treated with a solution of a metal salt whereby a mesostructured polymer gel loaded with metal ions is obtained. In such ion-exchanging step, the ions attached to the polymer, commonly H+ or NH +, are exchanged against the metal ions. In such step, the pH of the solution may be adjusted to 7 to 12 by adding a base such as ammonia. The temperature in the ion-exchanging step may be about 25°C to 100°C, the reaction time may be about 0.5 to 48 hours.
As a catalytically active metal, any metal is suitable and is selected from Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Al, Mo, Se, Sn, Pt, Ru, Rh, Zr, Hf, Re, Pd, W, Ir, Os, Rh, Nb, Ta, Pb, Bi, Au, Ag, Sc, Y and preferably from Fe, Co, Ni, Pt, Ru, Rh and Pd. Co is most preferred.
The metal may be applied in the form of a salt and mixtures thereof, preferably in the form of a solution of a metal salt or a mixture thereof, which are later in the process converted to the metal, metal alloy or metal oxides, depending on the used metal. The metal may be used in an amount to provide a metal load of 0,1 wt% up to 30 wt.%, preferably 3 to 20 wt%, more preferred 5 to 15 wt.% referred to the final product.
In the next step, the obtained polymer gel loaded with metal ions is treated in a protective gas atmosphere, preferably at an elevated temperature in the range of 400 °C to 1000 °C whereby a mesoporous carbon (MC) structure loaded with metal particles and/or metal oxide particles is obtained. A protective gas atmosphere is to be generally understood as an atmosphere which does not allow the oxidation of the MC support and may comprise a noble gas such as argon, helium, or an inert gas such as nitrogen or mixtures thereof, and hydrogen, which is preferably used in a volume ratio of 1 to 10 % hydrogen of the gas atmosphere. By means of the hydrogen content, the reduction of metal ions to metal particles can be supported.
In the additional step, the obtained mesoporous carbon structure is treated in a gas atmosphere with an oxygen content under conditions which are not oxidizing the MC support, preferably in a temperature range from 20 °C to 200 °C, more preferred at a temperature between 20 °C and 100 °C whereby a mesoporous carbon network structure loaded with catalytically active metal and/or metal oxide nanoparticles is obtained. In more detail, the treatment may be carried out in an atmosphere comprising protective gas and oxygen at temperature ranging from 20 °C to 200 °C for 5 min to 12 h, wherein the protective gas comprises nitrogen, helium, argon, or any mixture thereof and wherein the volume percentage of oxygen is about 0.1 to 10.
The present invention also refers to the mesoporous carbon loaded with metal oxide nanoparticles, obtainable according to the process of the present invention, in particular to the mesoporous carbon loaded with metal oxide nanoparticles, wherein the metal oxide nanoparticles have a particle size' in the range of 1 to 10 nm, preferably 2 to 6 nm, in particular 2.5 to 4.5 nm, for Co3O4 in particular from 2 to 5 nm, preferred 2 to 4 nm and most preferred from 2.5 to 3.5 nm, all measured from the TEM images and also calculated from the XRD data.
Thus, compared to the state of art, the surface area, pore volume, pore size and the size of Co particles are superior. For the material of the reference ChemElectroChem 2015, pages 2079-2088, for example, the surface area is <500 m2/g, the Co oxide size is ranging from 5 to 40 nm, and pore size is ranging from 2 to 4 nm. For the material of the present invention, the surface area is ranging from 500 to 1000 m2/g (BET), the pore size is centered at 6 to 15 nm, and the Co3O4 diameter is 2 to 5 nm. The diameters of the metal oxide particles were measured from the TEM image and correspond to the ones which are calculated based on XRD data.
Thus, the present invention refers to a mesoporous carbon structure/particles loaded with metal nanoparticles and/or metal oxide nanoparticles, obtainable according to the inventive processes, wherein the specific surface area is 500 m2/g
to 1000 m2/g, the mesopore size is centered at 6 to 15 nm, preferably 9 to 12 nm according to the nitrogen sorption measurement, the metal loading amount is ranging from 0.1 to 30 wt% referred to the total weight of the loaded MC support; and the particle size (diameter of the metal particles) is ranging from 1 to 10 nm.
Said mesoporous carbon supported Co3O4 nanoparticles can be preferably used as a catalyst, in particular as a catalytically active material in a process for transfer hydrogenation of a, β-un saturated aldehydes in the presence of the inventive catalyst and a H-donor, for example a secondary alcohol such as iso-propanol, to unsaturated alcohols as represented in the following scheme:
R1-CR2=CR3-CH=O → R1-CR2=CR3-CH2-OH, wherein R1 to R3 may be the same or different and may be selected each from Ci to C20 straight chain, branched chain or cyclic aliphatic hydrocarbons, optionally having one or more heteroatoms such as O, N, or S, in the chain or ring or unsaturated bonds such as CrC2o-alkyl, C2-C2o-alkenyl or C2-C2o-alkinyl, C3-C8- heterocycloalkyl or C6 to C2o aromatic hydrocarbon and partially arene- hydrogenated forms such as aryl, aryl-(Ci-C6)-alkyl, heteroaryl-(Ci-C6)-alkyl, each hydrocarbon optionally being substituted by one or more groups selected from Ci to C20 straight chain, branched chain or cyclic aliphatic hydrocarbons, optionally having one or more unsaturated bonds such as Ci-C2o-alkyl, C2-C2o-alkenyl or C2- C2o-alkinyl, or C6 to C20 aromatic hydrocarbon and partially arene-hydrogenated forms such as aryl, aryl-(Ci-C6)-alkyl, heteroaryl-(Ci-Ce)-alkyl or heterosubstituents, or wherein one of R1 or R2 may form a ring with R3, optionally having one or more heteroatoms in the ring, and the other of R1 or R2 is as defined before.
The invention is further illustrated by the attached drawings. In said drawings, Figure 1 shows a schematic representation of the inventive process;
Figure 2 shows a,b) TEM images (inset in Figure b shows the Co3O4 particle size distribution), c) SEM image, d-f) STEM, g) XRD pattern, h) XPS spectrum, and i)
N2 sorption isotherm of Co3O /MC (inset in Figure i shows the pore size distribution);
Figure 3 shows the structural characterization of mesoporous carbon pyrolysis at 800 °C: a, b) TEM images, and c, d) N2 isotherm and pore size distribution;
Figure 4 shows TEM images and XRD patterns of Co3O4 materials: a, b) Co3O4- nanocasting, c, d) Co3O4-6 nm, and e, f) Co3O4-17 nm;
Figure 5 shows a) catalytic performances for the transfer hydrogenation of cinnamaldehyde and citral over Co3O4 MC, b) the recycling results for transfer hydrogenation of FAL over Co3O4 MC.
Figure 6 shows a,b) TEM images of Co3O /MC after 6 runs, c) XRD patterns and d) N2 isotherms of Co3O4 MC before and after 6 runs.
Experimental Section Synthesis of C03O supported on mesoporous carbon (C03Q4/MC):
In a typical synthesis, 3.08 g of 2,4-dihydroxybenzoic acid, 0.6 g of ethylenediamine, 0.934 g of hexamethylentetramine (HMT) and 3.5 g of Pluronic P123 were dissolved in 80 ml_ of H2O. The solution was transferred into a teflon- lined stainless steel autoclave of 120 ml_ capacity, sealed and heated up to 130 °C and kept at that temperature for 4 h. Afterwards, the autoclave was allowed to cool down to room temperature. The polymer gel product was mashed and washed three times with deionized water. After dring at 50 °C over night, -5.77 g of polymer product was obtained. The polymer product was re-dispersed in 120 ml_ of solution (96 ml_ of H2O and 24 ml_ of ammonium hydroxide solution (28.0- 30.0%)) containing 4.62 mmol (1 .345 g) of Co(NO3)2-6H2O, stirred at 50 °C for 6 h. Then, the product was collected by filtration, washed three times with deionized water and dried at 50 °C under vacuum for 8 h. Finally, ~1 .64 g of Co3O4 MC was obtained by pyrolysis under H2/Ar (5%/95%) atmosphere. The pyrolysis procedure used here was as follows: the sample was heated to 400 °C with a rate of 2 °C min"1 and kept at that temperature for 3 h, then heated to 500 °C with a rate of 1 °C min"1 and kept at that temperature for 2 h. Afterwards, the sample was allowed to cool to room temperature and passivate in a flow of 1 % oxygen in argon for 2 h.
For synthesis of MC without the metal load, the polymer gel product was directly carbonized by heating up to 800 °C with a heating rate of 2 °C min"1 and holding at that temperature for 3 h under argon atmosphere.
Synthesis of Co3O4-nanocastinq, Co O4-6 nm and Co O4-17 nm:
The Co3O -nanocasting was prepared completely according to the method reported in literature. Co3O4-6 nm and Co3O4-17 nm were synthesized via a hydrothermal approach according to literature1 For the synthesis of 6 nm Co3O4 nanoparticles, 0.5 g of Co(CH3COO)2-4H2O was first dissolved in 25 mL of ethanol. Then 2.5 mL of 25% ammonia was added under vigorous stirring. After 10 min the obtained slurry was transferred to a teflon-lined stainless steel autoclave of 45 mL capacity, sealed and maintained at 150 °C for 3 h. Afterwards the resulting black solid was collected by centrifuge, washed intensively with ethanol and water, and finally dried under vacuum at 50 °C for 8 h. For the synthesis of 17 nm Co3O4 nanoparticles, the solvent was changed to a mixture of water (10 mL) and ethanol (15 mL). The rest of experimental conditions remained the same.
Transfer hvdroqenation of substrates
For a typical run, 1 mmol of substrates, 10 mL of 2-propanol, 50 mg of Co3O4 MC and a magnet bar were placed in a glass vial (20 mL). The vial was flushed with argon and then tightly closed. The experiment was performed at 120 °C under magnetic stirring of 800 rpm in a stainless steel heating block. A small volume of sample (-0.1 mL) was periodically withdrawn and analyzed by GC-MS. 1 ,6- hexandiol was chosen as internal standard for FAL and HMF system, while n- decane was used as internal standard for cinnamaldehyde and citral. When increasing reaction temperature to 140 °C and 160 °C, the experiments were carried out in a stainless steel autoclave reactor with volume of 20 mL. The rest of experimental conditions remained the same. Characterizations
Transmission electron microscopy (TEM), scanning transmission electron microscopy (STEM) and scanning electron microscopy (SEM) analyses were carried out with Hitachi HF-2000 and Hitachi S-5500 microscopes, respectively. All
samples were prepared by dipping carbon-coated copper grids into the ethanol solutions with the solid products and drying them at room temperature.
Powder X-ray diffraction (XRD) was performed on a Stoe STADI P diffractometer operating in reflection mode with Cu Ka radiation using a secondary graphite monochromator.
Nitrogen sorption isotherms were measured with a Micromeritics ASAP 2010 adsorption analyzer at 77 K. Prior to the measurements, the sample was degassed at a temperature of 250 °C for 6 h.
The specific surface areas were calculated from the adsorption data in the relative pressure range of 0.05 to 0.3 using the Brunauer-Emmett-Teller (BET) method. Pore size distributions were determined with the Barrett-Joyner-Halenda (BJH) method from the adsorption branch (desorption data which are normally recommended, can be influenced by network percolation or cavitation effects). The total pore volume was estimated from the amount adsorbed at a relative pressure of 0.97.
X-ray photoelectron spectroscopy (XPS) measurements were carried out with a Kratos HSi spectrometer with a hemispherical analyzer. The monochromatized Al Ka X-ray source (E=1486.6 eV) was operated at 15 kV and 15 mA. An analyzer pass energy of 40 eV was applied for the narrow scans. Hybrid mode was used as lens mode. The base pressure during the experiment in the analysis chamber was 4x10"7 Pa. To account for charging effects of carbonized samples, the binding energy values were referred to C 1 s at 284.5 eV.
Elemental analysis was carried out at Mikrolab Kolbe (Hohenweg 17, D-45470, Mulheim an der Ruhr) by AAnalyst 200 Atomic Absorption Spectrometer (AAS).
Table S1. Selective hydrogenation of α,β-unsaturated aldehydes1'
Rate
148.2 (63%,
140 3 100 97
0.5h)
401.4 (57%,
160 1 100 98
0.167h)
2.29 Co304-6nm 24 46 97
(22%, 4h) 0.26
Co304-17nm 120 24 15 99 (15%,
57.5
140 12 100 98
(63%, 1 h)
133.3
160 6 100 99 (73%,
0.65
1 1 Co304-6nm 120 48 37 99 (19%,
12h)
0.10
12 Co304-17nm 120 48 1 1 99 (1 1 %,
[a] Reaction conditions: 1 mmol substrate, 10 imL 2-propanol, 50 mg Co304/MC (25 mg for Co304- nanocasting, Co304-6 nm and Co304-17 nm). All results were obtained from GC testing.
[b] The numbers in parentheses are the conversion and the reaction time for reaction rate estimation.
[c] Scale-up reaction: 1.16 g furfural, 100 mL 2-propanol, 500 mg Co304/MC.
As shown above, the inventors have developed a simple and scalable method, including steps of hydrothermal process, ion-exchanging and reducing/mild oxidizing, to synthesize metal oxide nanoparticles such as Co3O4 nanoparticles supported in the framework of the mesoporous carbon network. Benefiting from the ion-exchange process, where Co2+ ions can be introduced into the polymer framework homogenously, the Co3O4 nanoparticles with a diameter of ~3 nm were finely dispersed in the framework of MC after reduction and mild oxidation processes. The as-obtained Co3O4 MC is more efficient than Co3O4-nanocasting, Co3O -6 nm and Co3O -17 nm (Figure 4) as catalyst for the transfer hydrogenation of α,β-unsaturated aldehydes (Table 1 , Figure 5a). The selectivities towards unsaturated alcohols over Co3O4 MC are always higher than 97% at full conversion. Furthermore, the catalyst after reaction was filtrated and washed with 2-propanol, followed by drying and treating under H2/Ar at 300 °C for 2 h to remove residues from the surface of the used Co3O4 MC. In this way, the Co3O4 MC catalyst was recycled at least six times without loss of activity, indicating a high stability of Co3O4 MC under the reaction conditions (Figure 5b, 6). The gram-scale preparation of furfural alcohol over Co3O4 MC indicates that such catalytic system is scalable without pressure issue (Table 1 , entry 13). The as- obtained furfuryl alcohol can be used as polymer precursor directly without further purification to synthesize ordered mesoporous carbon (CMK-5).
Therefore, the present catalytic system for transfer hydrogenation of α,β- unsaturated aldehydes over Co3O /MC has the potential to be utilized in industry. In addition, the synthesis methodology of Co3O4 MC, which is also easy to scale up, may be further extended to design other metal or metal oxide catalysts supported on MC.
Claims
Process for preparing a mesoporous carbon structure loaded with catalytically active metal nanoparticles and/or metal oxide nanoparticles, comprising the following steps:
- reacting an aromatic compound having at least one -COOH group and having at least one hydroxyl group with an aldehyde in presence of an aliphatic amine, said amine having 2 to 12 carbon atoms and at least two amine groups, and an amphiphilic triblock copolymer surfactant under hydrothermal conditions in molar ratios of 1 to 3 (aromatic compound) to 1 to 5 (aldehyde group) in the presence of the aliphatic amine (0.5 to 1 .5) and surfactant (0.03 to 0.09), whereby a mesostructured polymer gel is obtained,
- treating the obtained mesostructured polymer gel with a solution of a metal salt or with a mixture of different salts whereby a mesostructured polymer gel loaded with metal ions is obtained,
- treating the obtained polymer gel loaded with metal ions in a protective gas atmosphere at an elevated temperature in the range of 400 °C to 1000 °C whereby a mesoporous carbon structure loaded with catalytically active metal nanoparticles and/or metal oxide nanoparticles is obtained.
Process for preparing a mesoporous carbon structure loaded with catalytically active metal nanoparticles and/or metal oxide nanoparticles according to claim 1 , comprising the additional step of:
- treating the obtained mesoporous carbon structure in a gas atmosphere with an oxygen content under conditions which are not oxidizing the MC support, preferably in a temperature range from 20 °C to 200 °C, more preferred at a temperature between 20 °C and 100 °C whereby a mesoporous carbon network structure loaded with catalytically active metal and/or metal oxide nanoparticles is obtained.
Process for preparing a mesoporous carbon structure loaded with catalytically active metal and/or metal oxide nanoparticles, comprising the following steps:
- reacting an aromatic compound having at least one -COOH group and having at least one hydroxyl group with an aldehyde in presence of an aliphatic amine, said amine having 2 to 12 carbon atoms and at least two amine groups, and an amphiphilic triblock copolymer surfactant under hydrothermal conditions in molar ratios of 1 to 3 (aromatic compound) to 1 to 5 (aldehyde group) in the presence of the aliphatic amine (0.5 to 1 .5) and surfactant (0.03 to 0.09), whereby a mesostructured polymer gel is obtained,
- treating the obtained polymer gel in a protective gas atmosphere at an elevated temperature in the range of 400°C to 1000°C, whereby a mesoporous carbon structure is obtained,
- impregnating the obtained mesoporous carbon structure with a solution of a metal salt or with a mixture of different salts whereby a mesoporous carbon structure loaded with metal ions is obtained;
- treating the obtained mesoporous carbon structure loaded with metal ions in a protective gas atmosphere at an elevated temperature in the range of 200°C to 1000°C, optionally in the presence of hydrogen whereby a mesoporous carbon structure loaded with catalytically active metal nanoparticles and/or metal oxide nanoparticles is obtained.
Process for preparing a mesoporous carbon structure according to any of claims 1 to 3 wherein the surfactant is a poly(ethylene oxide)-poly(alkylene oxide)-poly (ethylene oxide) polymer wherein the alkylene oxide has at least three carbon atoms.
Process for preparing a mesoporous carbon structure according to any of claims 1 to 3 wherein the surfactant is a poly(ethylene oxide)-poly(propylene oxide)-poly (ethylene oxide) polymer.
Process for preparing a mesoporous carbon structure according to any of claims 1 to 5 wherein the metal is selected from Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Al, Mo, Se, Sn, Pt, Ru, Rh, Pd, W, Ir, Os, Rh, Zr, Hf, Re, Nb, Ta, Pb, Bi, Au, Ag, Sc, Y, preferably from Fe, Co, Ni, Pt, Ru, Rh and Pd, more preferred from Fe, Co, Ni, and most preferred Co.
7. Mesoporous carbon structure loaded with metal nanoparticles and/or metal oxide nanoparticles, obtainable according to the process of any of claims 1 to 6.
8. Mesoporous carbon structure loaded with metal nanoparticles and/or metal oxide nanoparticles, obtainable according to the process of any of claims 1 to 6 wherein the metal nanoparticles and/or metal oxide nanoparticles have a particle size in the range of 1 to 10 nm, preferably 2 to 6 nm, in particular 2.5 to 4.5 nm.
9. Use of the mesoporous carbon structure of claim 7 or 8 as a catalyst.
10. Use of the mesoporous carbon structure of claim 7 or 8 as a catalytically active material in a process for transfer hydrogenation of a, β-un saturated aldehydes to unsaturated alcohols in the presence of a H-donor as represented in the following scheme:
R1-CR2=CR3-CH=O → R1-CR2=CR3-CH2-OH, wherein R1 to R3 may be the same or different and may be selected each from Ci to C2o straight chain, branched chain or cyclic aliphatic hydrocarbons, optionally having one or more heteroatoms such as O, N, or S, in the chain or ring or unsaturated bonds such as CrC2o-alkyl, C2-C20- alkenyl or C2-C2o-alkinyl, Cs-Cs-heterocycloalkyl or C6 to C20 aromatic hydrocarbon and partially arene-hydrogenated forms such as aryl, aryl-(Ci - C6)-alkyl, heteroaryl-(Ci-C6)-alkyl, each hydrocarbon optionally being substituted by one or more groups selected from Ci to C20 straight chain, branched chain or cyclic aliphatic hydrocarbons, optionally having one or more unsaturated bonds such as Ci -C2o-alkyl, C2-C2o-alkenyl or C2-C2o- alkinyl, or C6 to C20 aromatic hydrocarbon and partially arene-hydrogenated forms such as aryl, aryl-(Ci-C6)-alkyl, heteroaryl-(Ci -C6)-alkyl or heterosubstituents, or wherein one of R1 or R2 may form a ring with R3,
optionally having one or more heteroatoms in the ring, and the other of R1 or R2 is as defined before.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP16172337.4A EP3251747A1 (en) | 2016-05-31 | 2016-05-31 | Process for preparing mesoporous carbon loaded with catalytically active metal and/or metal oxide nanoparticles for the selective transfer hydrogenation of alpha-beta-unsaturated aldehydes to unsaturated alcohols |
EP16172337.4 | 2016-05-31 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2017207555A1 true WO2017207555A1 (en) | 2017-12-07 |
Family
ID=56137096
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/EP2017/063012 WO2017207555A1 (en) | 2016-05-31 | 2017-05-30 | Preparation of mesoporous carbon with catalytically active metal oxide nanoparticles for the selective hydrogenation of alpha-beta-unsaturated aldehydes |
Country Status (2)
Country | Link |
---|---|
EP (1) | EP3251747A1 (en) |
WO (1) | WO2017207555A1 (en) |
Cited By (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN111001418A (en) * | 2019-12-18 | 2020-04-14 | 宁波林松信息科技有限公司 | Preparation method and application of high-efficiency silver-nickel hydroxide catalyst |
CN111116526A (en) * | 2019-12-16 | 2020-05-08 | 西南林业大学 | Method for preparing furfuryl alcohol by catalyzing hydrogenation of bio-based furfural through MOF-based catalyst |
CN111468154A (en) * | 2019-01-23 | 2020-07-31 | 中国石油化工股份有限公司 | Carbon-coated transition metal nanocomposite and preparation method and application thereof |
CN111468118A (en) * | 2019-01-23 | 2020-07-31 | 中国石油化工股份有限公司 | Carbon-coated transition metal nanocomposite and preparation method and application thereof |
CN111574483A (en) * | 2020-05-19 | 2020-08-25 | 中山大学 | Preparation method of 2, 5-furandimethanol |
WO2021121088A1 (en) * | 2019-12-20 | 2021-06-24 | 常州工学院 | Mesoporous carbon material loaded cobalt-based catalyst and preparation method therefor |
CN113617355A (en) * | 2021-07-30 | 2021-11-09 | 复旦大学 | Functional mesoporous material embedded with nano particles and in-situ embedding assembly method and application thereof |
WO2023024254A1 (en) * | 2021-08-26 | 2023-03-02 | 广东工业大学 | Embedded hydrothermal-resistant nisn-cs nanocatalyst, preparation method therefor and application thereof |
Families Citing this family (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN108821257B (en) * | 2018-05-02 | 2021-11-16 | 福建农林大学 | Lotus leaf-based binary mesoporous-microporous multilevel structure biochar and preparation method and application thereof |
CN109173988A (en) * | 2018-08-20 | 2019-01-11 | 扬州大学 | Magnetic coupling active carbon, preparation method and its application in treatment of Organic Wastewater |
CN109569625B (en) * | 2018-12-24 | 2021-06-29 | 河北工业大学 | Method for preparing supported metal nickel-based catalyst |
CN111499603B (en) * | 2019-01-23 | 2022-12-13 | 云南大学 | Method for preparing furfuryl alcohol by catalytic conversion of furfural |
CN111686820B (en) * | 2019-03-15 | 2023-07-21 | 中国石油化工股份有限公司 | Supported catalyst, preparation method and application thereof and preparation method of alkylene oxide |
CN112691659B (en) * | 2019-10-22 | 2023-04-28 | 中国科学院青岛生物能源与过程研究所 | Method for preparing mesoporous carbon-supported metal nanoparticle catalyst |
CN110975916B (en) * | 2019-12-09 | 2022-07-12 | 万华化学集团股份有限公司 | Catalyst for selective hydrogenation of olefinic unsaturated carbonyl compounds, preparation method and application thereof |
Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20110223494A1 (en) * | 2010-03-12 | 2011-09-15 | Energ2, Inc. | Mesoporous carbon materials comprising bifunctional catalysts |
WO2015175584A1 (en) * | 2014-05-13 | 2015-11-19 | Georgia-Pacific Chemicals Llc | Activated carbon products and methods for making and using same |
-
2016
- 2016-05-31 EP EP16172337.4A patent/EP3251747A1/en not_active Withdrawn
-
2017
- 2017-05-30 WO PCT/EP2017/063012 patent/WO2017207555A1/en active Application Filing
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20110223494A1 (en) * | 2010-03-12 | 2011-09-15 | Energ2, Inc. | Mesoporous carbon materials comprising bifunctional catalysts |
WO2015175584A1 (en) * | 2014-05-13 | 2015-11-19 | Georgia-Pacific Chemicals Llc | Activated carbon products and methods for making and using same |
Non-Patent Citations (7)
Title |
---|
CHEMELECTROCHEM, 2015, pages 2079 - 2088 |
JIAN LIU ET AL: "Molecular-based design and emerging applications of nanoporous carbon spheres", NATURE MATERIALS, vol. 14, no. 8, 23 July 2015 (2015-07-23), GB, pages 763 - 774, XP055340573, ISSN: 1476-1122, DOI: 10.1038/nmat4317 * |
JING WEI ET AL: "A Controllable Synthesis of Rich Nitrogen-Doped Ordered Mesoporous Carbon for CO 2 Capture and Supercapacitors", ADVANCED FUNCTIONAL MATERIALS, vol. 23, no. 18, 13 May 2013 (2013-05-13), DE, pages 2322 - 2328, XP055325322, ISSN: 1616-301X, DOI: 10.1002/adfm.201202764 * |
KRISTIINA KREEK ET AL: "Cobalt-Containing Nitrogen-Doped Carbon Aerogels as Efficient Electrocatalysts for the Oxygen Reduction Reaction", CHEMELECTROCHEM, vol. 2, no. 12, 15 September 2015 (2015-09-15), pages 2079 - 2088, XP055298622, ISSN: 2196-0216, DOI: 10.1002/celc.201500275 * |
ROJAS-CERVANTES MARÍA LUISA: "Some strategies to lower the production cost of carbon gels", JOURNAL OF MATERIALS SCIENCE, KLUWER ACADEMIC PUBLISHERS, DORDRECHT, vol. 50, no. 3, 9 October 2014 (2014-10-09), pages 1017 - 1040, XP035414704, ISSN: 0022-2461, [retrieved on 20141009], DOI: 10.1007/S10853-014-8617-1 * |
SAMANT P V ET AL: "Carbon supports for methanol oxidation catalyst", JOURNAL OF POWER SOURCES, ELSEVIER SA, CH, vol. 151, 10 October 2005 (2005-10-10), pages 79 - 84, XP027756638, ISSN: 0378-7753, [retrieved on 20051010] * |
WANG XIN ET AL: "Mesoporous carbons: recent advances in synthesis and typical applications", RSC ADVANCES: AN INTERNATIONAL JOURNAL TO FURTHER THE CHEMICAL SCIENCES, vol. 5, no. 101, 14 September 2015 (2015-09-14), GB, pages 83239 - 83285, XP055298088, ISSN: 2046-2069, DOI: 10.1039/C5RA16864C * |
Cited By (11)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN111468154A (en) * | 2019-01-23 | 2020-07-31 | 中国石油化工股份有限公司 | Carbon-coated transition metal nanocomposite and preparation method and application thereof |
CN111468118A (en) * | 2019-01-23 | 2020-07-31 | 中国石油化工股份有限公司 | Carbon-coated transition metal nanocomposite and preparation method and application thereof |
CN111116526A (en) * | 2019-12-16 | 2020-05-08 | 西南林业大学 | Method for preparing furfuryl alcohol by catalyzing hydrogenation of bio-based furfural through MOF-based catalyst |
CN111116526B (en) * | 2019-12-16 | 2022-10-11 | 西南林业大学 | Method for preparing furfuryl alcohol by hydrogenation of bio-based furfural under catalysis of MOF (Metal organic framework) -based catalyst |
CN111001418A (en) * | 2019-12-18 | 2020-04-14 | 宁波林松信息科技有限公司 | Preparation method and application of high-efficiency silver-nickel hydroxide catalyst |
CN111001418B (en) * | 2019-12-18 | 2022-06-24 | 中国兵器科学研究院宁波分院 | Preparation method and application of high-efficiency silver-nickel hydroxide catalyst |
WO2021121088A1 (en) * | 2019-12-20 | 2021-06-24 | 常州工学院 | Mesoporous carbon material loaded cobalt-based catalyst and preparation method therefor |
CN111574483A (en) * | 2020-05-19 | 2020-08-25 | 中山大学 | Preparation method of 2, 5-furandimethanol |
CN111574483B (en) * | 2020-05-19 | 2023-05-16 | 中山大学 | Preparation method of 2, 5-furandimethanol |
CN113617355A (en) * | 2021-07-30 | 2021-11-09 | 复旦大学 | Functional mesoporous material embedded with nano particles and in-situ embedding assembly method and application thereof |
WO2023024254A1 (en) * | 2021-08-26 | 2023-03-02 | 广东工业大学 | Embedded hydrothermal-resistant nisn-cs nanocatalyst, preparation method therefor and application thereof |
Also Published As
Publication number | Publication date |
---|---|
EP3251747A1 (en) | 2017-12-06 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
WO2017207555A1 (en) | Preparation of mesoporous carbon with catalytically active metal oxide nanoparticles for the selective hydrogenation of alpha-beta-unsaturated aldehydes | |
Liu et al. | One-step fabrication of Ni-embedded hierarchically-porous carbon microspheres for levulinic acid hydrogenation | |
EP2495042B1 (en) | PREPARATION AND APPLICATION of a TUNGSTEN CARBIDE CATALYST SUPPORTED ON MESOPOROUS CARBON | |
Ertas et al. | Metal-organic framework (MIL-101) stabilized ruthenium nanoparticles: Highly efficient catalytic material in the phenol hydrogenation | |
Hamdy et al. | New catalyst with multiple active sites for selective hydrogenolysis of cellulose to ethylene glycol | |
Gao et al. | Phosphomolybdic acid functionalized covalent organic frameworks: Structure characterization and catalytic properties in olefin epoxidation | |
Tang et al. | One-pot self-assembly synthesis of Ni-doped ordered mesoporous carbon for quantitative hydrogenation of furfural to furfuryl alcohol | |
Liu et al. | Tunable and selective hydrogenation of furfural to furfuryl alcohol and cyclopentanone over Pt supported on biomass-derived porous heteroatom doped carbon | |
Zhao et al. | Palladium nanoparticles anchored on sustainable chitin for phenol hydrogenation to cyclohexanone | |
Wang et al. | Sn-doped Pt catalyst supported on hierarchical porous ZSM-5 for the liquid-phase hydrogenation of cinnamaldehyde | |
Salameh et al. | Monodisperse platinum nanoparticles supported on highly ordered mesoporous silicon nitride nanoblocks: superior catalytic activity for hydrogen generation from sodium borohydride | |
Ghosh et al. | A green approach for the preparation of a surfactant embedded sulfonated carbon catalyst towards glycerol acetalization reactions | |
CN111437870A (en) | Metal @ MFI multi-level pore structure encapsulated catalyst and encapsulation method and application thereof | |
Hu et al. | Three‐Dimensionally Hierarchical Pt/C Nanocomposite with Ultra‐High Dispersion of Pt Nanoparticles as a Highly Efficient Catalyst for Chemoselective Cinnamaldehyde Hydrogenation | |
JP2011520608A (en) | Metal platinum silica supported catalyst and method for adjusting the same | |
Ren et al. | Pd@ MIL-101 as an efficient bifunctional catalyst for hydrodeoxygenation of anisole | |
Zhu et al. | Highly efficient catalytic transfer hydrogenation of furfural over defect-rich amphoteric ZrO 2 with abundant surface acid–base sites | |
CN110652983A (en) | Catalyst for hydrogenolysis of polyhydric alcohol and process for producing 1, 3-propanediol using the same | |
Li et al. | Renewable tar-derived Pd@ biocarbon for mild and efficient selectively hydrodeoxygenation of vanillin | |
Ren et al. | Selective aerobic oxidation of 5-hydroxymethylfurfural to 2, 5-dimethylfuran over heteroatom-doped ordered carbon supported Ru catalysts | |
CN111604051A (en) | Lignin-based ordered mesoporous carbon catalyst and preparation method and application thereof | |
CN113976167B (en) | Preparation method and application of Pd/HY molecular sieve and method for selectively loading metal on hierarchical pore molecular sieve | |
CN110496618B (en) | Isobutane dehydrogenation catalyst, preparation method thereof and method for preparing isobutene through isobutane dehydrogenation | |
Saadaoui et al. | Direct conversion of glucose to 5-hydroxymethylfurfural over niobium oxide/phosphate-carbon composites derived from hydrothermal carbonization of cyclodextrins | |
CN107469844B (en) | Catalyst with deoxidation and hydrogenation functions, preparation method thereof and deoxidation and hydrogenation method of carbonyl compound |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 17730410 Country of ref document: EP Kind code of ref document: A1 |
|
NENP | Non-entry into the national phase |
Ref country code: DE |
|
122 | Ep: pct application non-entry in european phase |
Ref document number: 17730410 Country of ref document: EP Kind code of ref document: A1 |